Synthesis, characterization, and catalytic behaviours of β-carbonylenamine-derived [O-NS]TiCl3 complexes in ethylene homo- and copolymerization

Article abstract of DOI:10.1039/b910868h

A series of [O^-NS]TiCl₃ complexes 5a-l derived from β-carbonylenamine were synthesized and characterized. In the presence of modified methylaluminoxane (MMAO), complexes 1, 5a-i and 5l are highly active for ethylene polymerization an

Full text of DOI:10.1039/b910868h

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PAPER
www.rsc.org/dalton | Dalton Transactions
Synthesis, characterization, and catalytic behaviours
of b-carbonylenamine-derived [O-NS]TiCl3 complexes in ethylene
homo- and copolymerization†
Xiao-Hong Yang, Zheng Wang, Xiu-Li Sun* and Yong Tang*
Received 2nd June 2009, Accepted 28th July 2009
First published as an Advance Article on the web 20th August 2009
DOI: 10.1039/b910868h
A series of [O-NS]TiCl3 complexes 5a–l derived from b-carbonylenamine were synthesized and
characterized. In the presence of modified methylaluminoxane (MMAO), complexes 1, 5a–i and 5l are
highly active for ethylene polymerization and copolymerization of ethylene with 1-hexene, CPE and
NBE. Up to 5.12 ¥ 106 g mol-1 h-1 atm-1 of activity for the copolymerization of ethylene with 1-hexene is
achieved with a 28.9 mol% incorporation ratio.
direct activity evaluation. By this strategy, titanium complex 1
Introduction
(Fig. 2) was synthesized and proved to be highly active toward
ethylene polymerization.8g Based on these results, the newly-
designed b-carbonylenamines-derived titanium complexes 5a–l
were synthesized very recently. Further studies show that such
complexes exhibit better copolymerization capability than the
corresponding salicylaldehyde-derived complexes, especially in the
copolymerization of ethylene with cycloolefins. In this paper, we
will report the synthesis, characterization of the complexes as well
as their polymerization behaviours upon activation with MMAO
in detail.
Development of effective catalysts for olefin polymerization and
copolymerization is of great interest in both basic research and
industrial applications since the discovery of the Ziegler–Natta
catalyst.1-3 Recently, considerably attention has been paid to single-
site non-metallocene catalysts due to their elegant capability
to catalyze the olefin polymerization and the copolymerization
of ethylene with a-olefins4 or cycloolefins5,6 allowing access to
previously inaccessible polymers.7
In our studies on the design and synthesis of olefin
polymerization catalysts,8 we reported salicylaldiminato-derived
[O-NX]TiCl3 (Fig. 1) complexes and their applications in olefin
polymerization in the presence of MMAO. Generally, it is
found that [O-NX]TiCl3/MMAO are highly active for ethy-
lene polymerization and for the copolymerization of ethylene/
a-alkenes and ethylene/cycloalkenes such as norbornene and
dicyclopentadiene.8b–f For such catalysts, steric hindrance around
titanium proves crucial for the copolymerization performance.8b–e
For instance, when X group was changed from –SPh to –SMe,
the copolymerization activity of ethylene/norbornene increased
10 times. We also developed a simple one pot method for
the screening of new titanium catalyst. This method allows us
to combine b-carbonylenamines with TiCl4(THF)2 in situ for
Fig. 2 b-Carbonylenamine-derived complex 1.
Results and discussion
Synthesis of [O-NS]TiCl3 5a–l
The desired b-carbonylenamine 4a–l were readily available
from the corresponding 1,3-diketones. Under the reaction
conditions without optimization, as shown in Table 1, 4a–l
could be prepared in moderate to good yields by treat-
ment of diketones with amines in the presence of cat-
alytic amount of 4-methylbenzenesulfonic acid (TsOH) in
toluene.
Fig. 1 Salicylaldiminato-derived [O-NX]TiCl3.
Complexes 5a–l were synthesized in two ways (Scheme 1).
One is to prepare the titanium complexes by the reaction of
b-carbonylenamine with TiCl4 directly in the absence of base.
1.2 equiv. of TiCl4 was mixed with 1.0 equiv. of the corresponding
enamine in toluene at -78 ◦C. The resulting mixture was warmed
to room temperature. After stirring for the desired time, the pure
complex was obtained in high yield by removal of the solvent, the
excess amount of TiCl4 and the produced HCl in vacuo (method
State Key Laboratory of Organometallic Chemistry, Shanghai Institute
of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road,
Shanghai, 200032, China. E-mail: tangy@mail.sioc.ac.cn
† Electronic supplementary information (ESI) available: 1H and 13C NMR
spectra along with X-ray crystallographic data. CCDC reference numbers
734045 and 734047. For ESI and crystallographic data in CIF or other
electronic format see DOI: 10.1039/b910868h
This journal is
The Royal Society of Chemistry 2009
Dalton Trans., 2009, 8945–8954 | 8945
©

Table 1 Synthesis of b-carbonylenamine 4a–la
2, 3, 4
R1
R2
R3
R4
R5
Yield (%)b
2a, 3a, 4a
2a, 3b, 4b
2a, 3c, 4c
2a, 3d, 4d
2a, 3e, 4e
2b, 3f, 4f
2c, 3f, 4g
2d, 3f, 4h
2e, 3f, 4i
2f, 3f, 4j
Ph
Ph
Ph
Ph
Ph
Ph
Ph
H
H
H
H
H
H
H
H
Ph
Ph
Ph
Ph
H
H
H
H
H
H
H
H
H
H
H
iPr
Me
77
50
55
61
77
75
67
77
78
37
41
32
iPr
nC8H17
nC18H37
Ph
Ph
Me
p-CF3C6H4
p-CH3C6H4
p-OCH3C6H4
Ph
nPr
nPr
p-CH3C6H4
p-OCH3C6H4
Ph
Ph
Ph
nPr
H
nPr
Bn
Me
H
nPr
2g, 3f, 4k
2a, 3g, 4l
Ph
Ph
nPr
nPr
a Reaction conditions: 1,3-dione 2 (12.0 mmol), amine 3 (11.0 mmol), toluene (25 mL), 4-methylbenzenesulfonic acid hydrate (0.062 g, 0.33 mmol),
refluxing for 3 d. b Isolated yield.
A in Scheme 1). Of the complexes shown in Scheme 1, 5a, 5c–d
and 5f–i were prepared by this method. The second one is by the
deprotonation of b-carbonylenamine with KH, followed by the
treatment with TiCl4 (method B in Scheme 1). Complexes 5b, 5e
and 5j–5l were prepared in moderate yields by method B.
Characterization of b-carbonylenamines 4a-l and complexes 5a–l
The structures of the compounds 4a–e and 4h–l that are derived
from the symmetric diketones were well-characterized by 1H, 13
C
NMR, MS, elemental analysis, and IR. The 13C NMR spectra
of b-carbonylenamines 4a–i and 4l display a signal at around d
2
=
188 ppm, which is assigned to be C O group. Substituents at R
position (4j and 4k) cause downfield chemical shift of carbonyl
group to ca. 196 ppm. In the case that 1-phenylbutane-1,3-dione
was employed for the preparation of enamine, noticeably, only
one product 4f was isolated but it was difficult to determine the
structure by 1H NMR and 13C NMR since both carbonyl groups
might react with amine. Fortunately, crystal of a similar enamine
4m suitable for X-ray analysis,9 which is made from the same
diketone as 4f used, were developed from ethanol. As shown in
Fig. 3, X-ray crystallographic analysis shows clearly that 4m
was the product that acetyl group of 2b reacted with amine. In
the molecular structure of 4m, H–N1–C7–C8–C9–O1 form a six
member ring via an intramolecular hydrogen bond between H
˚
Fig. 3 The molecular structure of 4m. Selected bond lengths (A) and
angles (◦): S1–C1, 1.763(4); O1–C9, 1.254(4); N1–C7, 1.351(5); N1–C6,
1.420(5); C7–C8, 1.362(5); C8–C9, 1.419(5); C1–S1–C17, 105.91(19);
C7–N1–C6, 130.2(4); C1–S1–C17, 105.91(19).
˚
and O1. The C9–O1 bond length is 1.254(4) A, much shorter
than the typical C–O single bond. C7–N1 bond length is 1.351(5)
˚
A, showing clearly that the C–N bond is a single bond. Thus,
and its purification was performed readily by recrystallization in
toluene.10
4m exists in b-carbonylenamine form. Combining these results
together with the fact that 13C NMR signals of the carbonyl group
The structures of the complexes 5a–l were also well-
characterized by 1H, 13C NMR, elemental analysis, and IR. From
13C NMR analysis of titanium complexes 5, the chemical shift
higher than 180 ppm was disappeared and two signals at around
170 ppm were observed, suggesting no carbonyl group in the
complexes. This observation is consistent with the X-ray study
of 5b.9 As shown in Fig. 4, X-ray crystallographic analysis of 5b
=
and N–C C unit in 4m are similar to the correspondent in 4f
(188.93 vs. 187.66 and 163.21 ppm vs. 164.14 ppm), the structure
of 4f was determined. The diarylketone 2c reacted with amine
3f affording a mixture with a ratio of 1/2, which could not be
separated by column chromatography. Fortunately, the mixture
of enamines could be used for the preparation of complex 5g
8946 | Dalton Trans., 2009, 8945–8954
This journal is
The Royal Society of Chemistry 2009
©

Table 2 The crystal data and details of data collections for 4m and 5ba
Data
4m
5b
Formula
FW
C24H23NOS
373.49
C20H22Cl3NOSTi
478.70
Crystal size/mm
Crystal system
Space group
0.369 ¥ 0.278 ¥ 0.125
Monoclinic
P21/c
21.6646(19)
8.0100(7)
24.360(2)
90
106.432(2)
90
4054.6(6)
8
0.486 ¥ 0.092 ¥ 0.070
Monoclinic
P21/c
7.0434(10)
11.2130(15)
28.939(4)
90
96.423(3)
90
2271.2(5)
4
˚
a/A
˚
b/A
˚
c/A
a/◦
b/◦
g /◦
3
˚
V/A
Z
Dc/Mg m-3
1.224
0.173
27.50
1.400
0.832
27.00
m/mm-1
◦
qmax
/
Reflections
23 753/9119
[Rint = 0.1314]
0.881
R1 = 0.0654,
wR2 = 0.1749
R1 = 0.1590,
wR2 = 0.1931
13 122/4923
[Rint = 0.0548]
0.921
R1 = 0.0503,
wR2 = 0.0842
R1 = 0.0846,
wR2 = 0.0928
collected/unique
Goodness-of-fit on F2
Final R indices
[I > 2(I)]
R indices (all data)
a Data collections for compounds were performed at 20 ◦C on a Bruker
SMART diffractometer with graphite-monochromated Mo Ka radiation
˚
(l = 0.71073 A). The SADABS absorption correction was applied. The
structure were solved by direct methods and refined on F2 by full-matrix
least squares techniques with anisotropic thermal parameters for non-
hydrogen atoms. Hydrogen atoms were placed at the calculated positions
and were included in the structure calculation without further refinement
of the parameters. All calculations were carried out using the SHELXS-97
program.
Scheme 1 Synthesis of complexes 5a–l.
revealed that the ligand coordinated titanium atom with enolate
oxygen, imine nitrogen, and sulfur atom. C9–O1 and C7–N1
˚
˚
bond lengths are 1.330(3) A and 1.309(4) A, respectively. The
geometry around titanium atom is a distorted octahedral with
three chlorine ligands in a mer disposition. Of which, the bond
angles of Cl1–Ti–Cl3, Cl2–Ti–Cl3, and Cl1–Ti–Cl2 are 165.43(4),
93.68(4), and 93.26(4)◦, respectively. This geometry is favorable
for the olefin coordination and insertion. The sulfur atom in
5b is sp3-hybridized, with S1–C2 being roughly perpendicular to
the S1-containing five-membered ring. The Ti–S1 bond length is
˚
Fig. 4 The molecular structure of 5b. Selected bond lengths (A)
and angles (◦): S1–C1, 1.806(3); O1–C9, 1.330(3); N1–C7, 1.309(4);
N1–C6, 1.468(4); C7–C8, 1.429(4); C8–C9, 1.351(4); Ti–O1, 1.827(2);
Ti–N1, 2.148(2); Ti–Cl2, 2.2720(10); Ti–Cl1, 2.2902(10); Ti–Cl3,
2.3293(9); Ti–S1, 2.6413(10); C1–S1–C2, 101.97(15); C7–N1–C6, 119.9(3);
O1–Ti–N1, 84.12(9); O1–Ti–Cl2, 103.24(7); O1–Ti–Cl1, 98.92(7);
N1–Ti–Cl1, 87.72(7); O1–Ti–Cl3, 91.93(7); Cl1–Ti–Cl3, 165.43(4);
Cl2–Ti–Cl1, 93.26(4); Cl2–Ti1–Cl3, 93.68(4); S1–C1–C6–N1, -59.7(3);
C14–C7–C8–C9, -176.5(3); N1–C7–C8–C9, 5.7(5); S1–C1–C6–N1,
-59.7(3).
2.6413(10) A, which is longer than that in 1 (2.5953 A)8g as well as
those in salicylaldiminato-derived [O-NS]TiCl3 complexes.8c Crys-
tal data and details of data collection and structure refinements
were given in Table 2.
˚
˚
shown in Table 3, the structure of the complexes influenced the
ethylene polymerization behaviours including both the catalytic
activity and the molecular weight of the resulting polyethylene.
Complexes 1 and 5a–d gave similar activities and molecular
weights, suggesting that the steric hindrance of substituent R5
on sulfur atom has almost no effect on the behaviours of ethylene
Ethylene homopolymerization
Upon activation with MMAO (MMAO/Ti = 1000/1) in toluene,
complexes 5a–l were investigated for ethylene polymerization. As
This journal is
The Royal Society of Chemistry 2009
Dalton Trans., 2009, 8945–8954 | 8947
©

50 ◦C resulted in a decrease of activity and an increase of 1-hexene
incorporation ratio (entry 2 vs. 3). The catalyst performance was
Al/Ti molar ratio-dependent. High activity could be achieved with
500 Al/Ti molar ratio. Increasing the Al/Ti molar ratio from 500
to 2000 further improved activity obviously and increased the
1-hexene incorporation but decreased the molecular weight (en-
tries 2 and 4–6). With increasing the amount of comonomer feed,
the copolymerization activity almost maintained while the content
of 1-hexene in the copolymer increased rapidly (entries 2, 7–9).
Besides 1-hexene, other a-olefins such as 1-octene, 1-dodecene,
and 1-octadecene could be incorporated easily in the polyethylene
backbone with high activity (entries 11–13). It is worthy to note
that complex 1 exhibited much higher copolymerization capability
than the corresponding salicylaldehyde-derived imine titanium
complex 6 (Fig. 5), probably due to the much more open space
around titanium atom in 1 than in 6 (entry 14 vs. 2 and 15 vs.
9). As shown in Table 4, for example, 6/MMAO promoted the
copolymerization of ethylene/1-hexene in an activity of 1.98 ¥
106 g mol-1 of Ti h-1 atm-1 with 10.5 mol% 1-hexene incorporation
ratio. However, when 1 was employed instead of 6, the activity
and 1-hexene incorporation ratio were increased to 4.44 ¥ 106 g
mol-1 Ti h-1 atm-1 and 23.6 mol%, respectively, under the same
polymerization conditions (entry 9 vs. 15).
Table 3 Ethylene polymerization using complexes 5
Entrya
Cat.
PE/g
Activityb
Mw
Mw/Mn
c,d
c
1
2
3
4
5
6
7
8
9
10
11
12
13
14e
5a
18g
5b
5c
5d
5e
5f
0.83
0.99
0.84
0.86
0.88
0.51
0.63
0.73
0.94
0.95
Trace
Trace
0.53
1.72
1.66
1.98
1.68
1.72
1.76
1.02
1.26
1.46
1.88
1.90
—
12.7
10.4
12.6
11.1
12.7
33.6
14.9
22.2
14.8
29.6
—
2.03
2.75
3.05
2.65
2.91
2.14
2.82
2.19
2.62
2.12
—
5g
5h
5i
5j
5k
5l
—
1.06
0.57
—
16.2
10.1
—
2.10
2.75
5a
a 50 mL toluene, 3 mmol of cat., MMAO/Ti = 1000, 30 ◦C, 1 atm ethylene,
10 min. b 106 g mol-1 Ti h-1 atm-1. c Determined by GPC. d 104 g mol-1.
e 60 min.
polymerization (entries 1–5), which is similar to the corresponding
salicylaldiminato-derived catalysts.8f Replacement of alkyl group
with phenyl group on sulfur atom increased the molecular weight
but decreased the activity slightly (entries 1–5 vs. entry 6). The
catalytic activity was decreased from 1.98 ¥ 106 g mol-1 Ti h-1
atm-1 to 1.26 ¥ 106 g mol-1 Ti h-1 atm-1 when the substituent
R3 was changed from phenyl group to methyl group (entry 2
vs. 7). The activity of 5g with an electron-withdrawing group p-
CF3C6H4 at R3 position is slightly lower than that of 1 (entry
2 vs. 8). Similar catalytic activities were observed for 1, 5h and
5i, showing substituent effects at R1 and R3 positions are weak
(entry 2 vs. entries 9, 10). Noticeably, substitution of hydrogen
atom with methyl or benzyl group at R2 position resulted in loss
of activity (entry 2 vs. 11, 12). The reason is not clear. GPC studies
showed that the molecular weight distribution ranged from 2.03
to 3.05, similar to those of PE produced by a single site catalyst.
Catalytic activity decreased slightly when the polymerization time
was prolonged to 1 hour, probably due to the wrapping of catalytic
species by precipitated polyethylene (entry 14).
Fig. 5 Salicylaldehyde-derived imine titanium complex 6.
Ethylene copolymerization with cycloolefins
Ethylene/cycloolefin copolymerization might lead to important
high performance polymer materials with many unique properties.
Complexes 1 and 5a–b prove to catalyze the copolymerization
of ethylene with cycloolefins very efficiently. Both cyclopentene
(CPE) and norbornene (NBE) are suitable comonomers upon
activation with MMAO. As shown in Table 5, at the same initial
concentration of CPE and the same scale of complex 1, diluting
1 with toluene increased both the yield and Mw of the polymer
but the insertion ratio of CPE decreased obviously (entries 1–
3). Enhancing the initial concentration of CPE improved the
incorporation ratio of monomer (entries 3–6). For instance, the
CPE incorporation ratio doubled when the concentration of CPE
was increased from 2.0 M to 5.0 M, reaching 26.0 mol% (entry 3
vs. 6).12 Complexes 5a and 5b also exhibited good activity toward
the copolymerization of ethylene/CPE with good comonomer
incorporation ratio (entries 8–9). Comparing with 1, both 5a and
5b gave the copolymers under the same polymerization conditions
with higher molecular weight (entry 3 vs. entries 8 and 9). Similar
to the aforementioned copolymerization of ethylene with 1-
hexene, complex 1 is obviously superior to salicylaldehyde-derived
imine titanium complex 6 for the ethylene/CPE copolymerization.
Under the same conditions, 1 showed much higher activity and
much better comonomer incorporation than 6 (entry 3 vs. 10).
Ethylene copolymerization with a-olefins
The performance of a catalyst for copolymerization of ethylene
with a-olefin is very important. Using complex 1 as a model
catalyst, we investigated the copolymerization between ethylene
and a-olefins. As shown in Table 4, positive comonomer effects
were o◦bserved. For example, 1 catalyzed ethylene polymerization
at 30 C with 1000 Al/Ti ratio in an activity of 1.98 ¥ 106 g
mol-1 Ti h-1 atm-1 (entry 2, Table 3). However, under the same
polymerization conditions with complex 1 as a catalyst, the
activity of ethylene/hexene copolymerization was over 5.00 ¥
106 g mol-1 Ti h-1 atm-1 (entry 10, Table 4). The polymerization
temperature influenced the activity, molecular weight as well as
incorporation ratio of monomer (entry 1–3). For instance, the
copolymerization activity was 0.88 ¥ 106 g mol-1 Ti h-1 atm-1
at 0 ◦C. Raising the temperature from 0 to 25 ◦C increased the
activity to 4.34 ¥ 106 g mol-1 Ti h-1 atm-1 and decreased the Mw
from 58.6 ¥ 104 g mol-1 to 11.8 ¥ 104 g mol-1. The 1-hexene
incorporation ratio was also increased from 7.2 mol% to
11.1 mol% (entry 1 vs. 2).11 Further enhancing the temperature to
8948 | Dalton Trans., 2009, 8945–8954
This journal is
The Royal Society of Chemistry 2009
©

Table 4 Ethylene copolymerization with a-olefins
cd
c
Entrya
Comonomer/mmol
Polymer/g
Activitya
Mw
Mw/Mn
Incorporation ratio (mol%)e
1f
2
1-Hexene (12)
1-Hexene (12)
1-Hexene (12)
1-Hexene (12)
1-Hexene (12)
1-Hexene (12)
1-Hexene (6)
1-Hexene (24)
1-Hexene (36)
1-Hexene (36)
1-Octene (12)
1-Dodecene (12)
1-Octadecene (12)
1-Hexene (12)
1-Hexene (36)
0.44
2.17
1.42
1.44
2.01
2.11
2.20
2.47
2.22
2.56
1.59
1.80
2.02
0.88
0.99
0.88
4.34
2.84
2.88
4.02
4.22
4.40
4.94
4.44
5.12
3.18
3.60
4.04
1.76
1.98
58.6
11.8
10.4
21.8
11.7
8.6
11.2
15.7
15.2
10.3
18.8
19.6
21.4
18.3
21.5
1.85
2.22
2.10
2.05
2.15
2.01
2.20
2.22
2.20
1.94
2.06
2.11
2.13
2.06
1.83
7.2
11.1
16.7
13.2
14.2
17.1
8.6
18.0
23.6
28.9
10.0
7.2
3g
4h
5i
6j
7
8
9
10k
11
12
13
14l
15l
5.5
6.5
10.5
a Toluene (50 mL), 3 mmol of 1,◦1 atm of ethylene, 25 ◦C, MMAO/Ti = 1000, 10 min. b Activity, 106 g mol-1 h-1 at◦m-1. c Determined by GPC. d 104 g mol-1.
e Determined by 13C NMR. f 0 C. g 50 ◦C. h MMAO/Ti = 500. i MMAO/Ti = 1500. j MMAO/Ti = 2000. k 30 C. l 3 mmol of 6.
Table 5 Copolymerization of ethylene with cyclopentene and norbornenea
d,e
d
Entry
Cat.
Comonomer/mmol
Cb
Polymer/g
Activityc
Mw
Mw/Mn
Incorporation ratio f (mol%)
1
2
3
4
5
1
CPE (25)
CPE (50)
CPE(100)
CPE(100)
CPE(100)
CPE(100)
CPE(50)
CPE(100)
CPE(100)
CPE(100)
NBE(4)
NBE(6)
NBE(8)
NBE(10)
NBE(20)
NBE(30)
NBE(20)
2.0
2.0
2.0
3.0
4.0
5.0
3.3
2.0
0.56
0.68
0.97
0.77
0.65
0.53
1.20
0.97
0.83
0.59
1.14
0.70
0.65
0.37
0.28
0.17
0.97
0.93
1.13
1.62
1.28
1.08
0.88
3.00
1.62
1.38
0.98
22.80
14.00
13.00
7.40
5.60
3.40
19.40
4.1
5.6
7.2
3.4
5.5
4.9
5.4
10.1
11.1
10.1
24.4
42.8
44.8
23.1
15.8
11.9
31.3
1.74
1.70
1.57
1.77
1.77
1.62
2.11
2.08
2.13
1.84
2.10
1.85
1.91
1.55
1.60
1.75
1.70
24.0
21.1
12.8
17.3
21.3
26.0
29.7
7.2
1
1
1
1
6
1
7g
1
8
9
5a
5b
6
2.0
2.0
5.5
4.3
10
11h
12h
13h
14h
15h
16h
17h
1
0.08
0.12
0.16
0.20
0.40
0.60
0.40
11.2
26.0
30.6
39.7
44.2
45.6
29.8
1
1
1
1
1
6
a Toluene (50 mL), 12 mmol of cat., 30 ◦C, MMAO/Ti = 1000, 1 atm of ethylene, 30 min. b Concentration of the comonomer, mol L-1. c 105 g mol-1 Ti h-1
atm-1. d Determined by GPC. e 104 g mol-1. f Determined by 13C NMR. g 20 min. h 3 mmol cat., 10 min.
Since the performance of complex 1 for the copolymerization
of ethylene with CPE is better than complexes 5a and 5b, 1
was chosen as a catalyst to investigate the ethylene/norbornene
copolymerization. As shown in Table 5, both the incorporation
ratio and the activity depended on the initial concentration of
norbornene. With an increasing feed of norbornene from 4 to
30 mmol, the copolymerization activity was decreased strongly
but the molar incorporation ratio was increased to 45.6% at
1 atm of ethylene atmosphere (entries 11–16).13 When 4 mmol
of NBE (0.08 M) was used, an activity of 2.28 ¥ 106 g mol-1 Ti h-1
atm-1 and an incorporation of 11.2 mol% were obtained. With the
increase of the initial concentration of NBE, the molecular weight
of the copolymer increased first and then decreased. The highest
molecular weight was obtained when the concentration was
0.16 mol L-1 (entry 13). Remarkably, 0.16 M of NBE concentration
in the case of complex 1 gave a similar incorporation ratio to that
when 0.40 M of NBE concentration was employed using complex
6 as a catalyst (entry 15 vs. 17, Table 5). This result suggested that
compound 1 promote the copolymerization of ethylene with NBE
more efficient than 6.
Conclusions
The titanium complexes derived from b-carbonylenamine were
prepared and characterized. In the presence of MMAO, these
titanium complexes showed high activity toward ethylene poly-
merization. a-Alkene and cycloalkenes such as CPE and NBE
proved to incorporate into polyethylene backbone efficiently with
an activity of up to 5.12 ¥ 106 g mol-1 Ti h-1 atm-1, affording
copolymers with tunable contents of the comonomer. By changing
the comonomer initial concentration and polymerization condi-
tions, the high incorporation ratios of CPE and NBE could be
achieved with up to 29.7 mol% and 45.6 mol%, respectively. Higher
activity and better incorporation capability of b-carbonylenamine
derived [O-NS]TiCl3 complexes than that of the corresponding
salicylaldiminato-derived complex 6 were demonstrated.
This journal is
The Royal Society of Chemistry 2009
Dalton Trans., 2009, 8945–8954 | 8949
©

7.91–7.88 (m, 2 H), 7.48–7.36 (m, 8 H), 5.78 (s, 1 H), 3.43 (ABd,
J = 7.2 Hz, 1 H), 3.38 (ABd, J = 6.6 Hz, 1 H), 2.64 (t, J =
7.5 Hz, 2 H), 2.38 (t, J = 7.2 Hz, 2 H), 1.50–1.43 (m, 2 H), 1.43–
1.25 (m, 12 H), 0.88 (t, J = 6.9 Hz, 3 H). 13C NMR (75 MHz,
CDCl3): d 188.58, 166.37, 140.06, 135.44, 130.76, 129.49, 128.57,
128.15, 127.71, 127.06, 93.83, 44.32, 32.69, 32.08, 31.76, 29.57,
29.15, 29.12, 28.80, 22.62, 14.08. IR (KBr) v (cm-1): 3060, 2925,
2854, 1595, 1584, 1570, 1480, 1331, 1295, 1225, 1143, 1057, 1025,
748, 691, 612. C25H33NOS (395.6): calcd C 75.90, H 8.41, N 3.54.
Found C 76.10, H 8.50, N 3.36. MS (ESI) (m/z): 396 (M + H+).
Experimental
General considerations
All manipulations of air- and/or moisture-sensitive compounds
were performed under nitrogen atmosphere using standard
Schlenk techniques. 1H NMR and 13C NMR spectra were recorded
on a Varian XL-300 MHz or 400 MHz spectrometer with TMS
as the internal standard. Mass spectra were obtained using
a HP5959A spectrometer. IR spectra were recorded using a
Nicolet AV-360 spectrometer. Elemental analysis was performed
by the Analytical Laboratory of Shanghai Institute of Organic
Chemistry (CAS). Mn, Mw, and Mw/Mn values of polymers were
determined with a Waters Alliance GPC 2000 series at 135 ◦C
(polystyrene calibration, 1,2,4-trichlorobenzene as a solvent at
a flow rate of 0.92 mL min-1). 13C NMR data of polymer was
obtained using o-dichlorobenzene-d4 as a solvent at 110 ◦C. X-
Ray crystallographic data were collected using a Bruker AXSD8
X-Ray diffractometer. Toluene, THF, and hexane were distilled
over sodium/benzophenone ketyl prior to use. Dichloromethane
was distilled over CaH2. Modified methylaluminoxane (MMAO)
was purchased from Akzo Chemical as a 1.9 M toluene solution.
Polymerization-grade ethylene was purified before use. The com-
plex 18g and 68f were prepared according to the literature methods
reported.
(Z)-3-(2-(octadecylthio)ethylamino)-1,3-diphenylprop-2-en-1
-one (4d). The same procedure◦as that for the preparation of 4a.
Yield: 0.61 g (61%). M.p: 42–44 C. 1H NMR (300 MHz, CDCl3):
11.46 (brs, 1 H), 7.91–7.88 (m, 2 H), 7.47–7.37 (m, 8 H), 5.78 (1
H), 3.43 (ABd, J = 6.6 Hz, 1 H), 3.38 (ABd, J = 6.9 Hz, 1 H),
2.63 (t, J = 6.9 Hz, 2 H), 2.37 (t, J = 6.9 Hz, 2 H), 1.50-1.43
(m, 2 H), 1.40-1.20 (m, 30 H), 0.88 (t, J = 6.6 Hz, 3 H). 13C
NMR (75 MHz, CDCl3): 188.59, 166.38, 140.06, 135.44, 130.77,
129.49, 128.56, 128.16, 127.71, 127.06, 93.83, 44.31, 32.69, 32.08,
31.89, 30.92, 29.67, 29.63, 29.57, 29.50, 29.34, 29.18, 28.81, 22.66,
14.11. IR (KBr) v (cm-1): 3061, 2923, 2852, 2386, 1596, 1584, 1570,
1517, 1480, 1329, 1295, 1223, 1143, 1055, 1025, 748. C35H53NOS
(535.87): calcd C 78.45, H 9.97, N 2.61. Found C 78.31, H 9.67,
N 2.49. MS (EI) (m/z): 535 (M+).
(Z)-1,3-diphenyl-3-(2-(phenylthio)ethylamino)prop-2-en-1-one
(4e). The same procedure as that for the preparation of 4a. Yield:
The synthesis of the new compounds
◦
1
1.80 g (77%). M.p: 50–61 C. H NMR (300 MHz, CDCl3): d
11.48 (s, 1 H), 7.90 (dd, J = 1.5 Hz, 7.5 Hz, 2 H), 7.44-7.18
(m, 13 H), 5.78 (s, 1 H), 3.45-3.38 (m, 2 H), 3.02-2.98 (m, 2 H).
13C NMR (75 MHz, CDCl3): d 188.75, 166.29, 140.04, 135.27,
134.65, 130.84, 129.73, 129.50, 129.01, 128.62, 128.19, 127.66,
127.09, 126.44, 94.10, 43.58, 34.44. IR (KBr) v (cm-1): 3058, 2987,
1595, 1569, 1480, 1331, 1296, 1057, 1025, 743, 691. C23H21NOS
(359.48): calcd C 76.85, H 5.89, N 3.90. Found C 76.62, H 5.99,
N 3.70. MS (ESI) (m/z): 360 (M + H+).
(Z)-3-(2-(methylthio)ethylamino)-1,3-diphenylprop-2-en-1-one
(4a). To a solution of 1,3-diphenylpropane-1,3-dione (2a, 2.71 g,
12.0 mmol) and 2-(methylthio)ethanamine (3a, 1.00 g, 11.0 mmol)
in toluene (25 mL) was added 4-methylbenzenesulfonic acid
hydrate (0.062 g, 0.33 mmol) at room temperature. The flask was
equipped with a water separator. After refluxing for 3 d, the solvent
was removed under reduced pressure and the residue was purified
by column chromatography on silica gel to give yellow solid. Yield:
2.53 g (77%). M.p.: 72–76 ◦C;1H NMR (300 MHz, CDCl3): d 11.47
(s, 1 H), 7.91–7.88 (m, 2 H), 7.48–7.36 (m, 8 H), 5.79 (s, 1 H), 3.44
(ABd, J = 6.9 Hz, 1 H), 3.40 (ABd, J = 6.9 Hz, 1 H), 2.63 (t,
J = 6.9 Hz, 2 H), 2.00 (s, 3 H). 13C NMR (100 MHz, CDCl3):
d 188.62, 166.39, 140.07, 135.47, 130.77, 129.50, 128.57, 128.15,
127.72, 127.07, 93.87, 43.63, 34.91, 15.46. IR (KBr) v (cm-1): 3058,
2915, 1595, 1583, 1569, 1480, 1331, 1295, 1225, 1143, 1057, 1025,
749, 692; MS (EI): m/z = 297 (M+); HRMS: 297 (C18H19NOS).
(Z)-1,3-diphenyl-3-(2-(isopropylthio)ethylamino)prop-2-en-1-
one (4b). The same procedure ◦as that for the preparation of 4a.
Yield: 3.20 g (50%). M.p: 66–71 C. 1H NMR (300 MHz, CDCl3):
d 11.45 (brs, 1 H), 7.91–7.88 (m, 2H), 7.47–7.37 (m, 8 H), 5.78 (s,
1 H), 3.42 (ABd, J = 6.9 Hz, 1 H), 3.37 (ABd, J = 6.6 Hz, 1 H),
2.81–2.76 (m, 1 H), 2.66 (t, J = 7.5 Hz, 2 H), 1.18 (d, J = 6.3 Hz, 6
H). 13C NMR (75 MHz, CDCl3): d 188.59, 166.34, 140.07, 135.41,
130.76, 129.50, 128.57, 128.16, 127.68, 127.03, 93.83, 44.60, 34.87,
31.11, 23.26. IR (KBr) v (cm-1): 3060, 2980, 1595, 1579, 1554,
1480, 1443, 1340, 1299, 1224, 1201, 1141, 1057, 747, 707, 691.
C20H23NOS (325.47): calcd C 73.81, H 7.12, N 4.30. Found: C
73.58, H 6.94, N 4.19. MS (ESI): m/z = 326 (M + H+).
(Z)-1-phenyl-3-(2-(propylthio)ethylamino)but-2-en-1-one (4f).
The same procedure as that for the preparation of 4a. Yield:
1
2.47 g (75%). H NMR (300 MHz, CDCl3): d 11.52 (s, 1 H),
7.87–7.85 (m, 2 H), 7.41–7.35 (m, 3 H), 5.69 (s, 1 H), 3.54 (ABd, J
= 6.6 Hz, 1 H), 3.49 (ABd, J = 7.2 Hz, 1 H), 2.74 (t, J = 6.9 Hz,
2 H), 2.55 (t, J = 7.2 Hz, 2 H), 2.09 (s, 3 H), 1.66–1.59 (m, 2 H),
0.99 (t, J = 7.2 Hz, 3 H). 13C NMR (75 MHz, CDCl3): d 187.66,
164.14, 140.08, 130.28, 127.93, 126.70, 92.24, 43.02, 34.23, 32.01,
22.77, 19.29, 13.22. IR (KBr) v (cm-1): 3059, 2961, 2927, 2870,
1602, 1584, 1552, 1521, 1441, 1322, 1294, 1229, 1085, 1064, 1027,
738. C15H21NOS (263.40): calcd C 68.40, H 8.04, N 5.32. Found
C 68.51, H 7.79, N 5.41. MS (EI) (m/z): 263 (M+).
(Z)-3-(2-(propylthio)ethylamino)-1,3-di-p-tolylprop-2-en-1-one
(4h). The same procedu◦re as that for the preparation of 4a. Yield:
1.06 g (77%). M.p: 64–68 C. 1H NMR (300 MHz, CDCl3): d 11.41
(s, 1 H), 7.79 (d, J = 8.1 Hz, 2 H), 7.31–7.18 (m, 6 H), 5.76 (s,
1 H), 3.40 (q, J = 6.6 Hz, 2 H), 2.62 (t, J = 6.9 Hz, 2 H), 2.41-
2.34 (m, 8 H), 1.54–1.47 (m, 2 H), 0.92 (t, J = 7.2 Hz, 3 H). 13
C
NMR (75 MHz, CDCl3): d 188.36, 166.31, 141.01, 139.55, 137.48,
132.66, 129.17, 128.84, 127.66, 127.07, 93.68, 44.31, 34.04, 32.61,
22.87, 21.39, 21.30, 13.34. IR (KBr) v (cm-1): 2960, 2920, 2869,
1590, 1582, 1561, 1509, 1488, 1329, 1301, 1228, 1180, 1142, 1063,
(Z) - 3 - (2 - (octylthio)ethylamino) - 1,3 - diphenylprop-2-en-1-one
(4c). The same procedure as that for the preparation of 4a. Yield:
1
1.15 g (55%). H NMR (300 MHz, CDCl3): d 11.46 (s, 1 H),
8950 | Dalton Trans., 2009, 8945–8954
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The Royal Society of Chemistry 2009
©

1018, 824, 772. C22H27NOS (353.52): calcd C 74.74, H 7.70, N
added dropwise a solution of (Z)-3-(2-(methylthio)ethylamino)-
1,3-diphenyl prop-2-en-1-one (4a) (0.66 g, 2.2 mmol) in toluene (7
mL) over 15 min. The resulting mixture was allowed to warm to
room temperature and stirred for 3 h. After removing the solvent
under reduced pressure, the brown-red solid was collected and
dried in vacuo to give the desired pure complex. Yield: 0.85 g
(85%). 1H NMR (400 MHz, CDCl3): d 7.84–7.82 (m, 2 H), 7.53–
7.40 (m, 6 H), 7.32–7.30 (m, 2 H), 6.39 (s, 1 H), 4.18–4.01 (m, 2 H),
3.26 (t, J = 10 Hz, 1 H), 2.78 (s, 3 H), 2.69 (d, J = 11.6 Hz, 1 H).
13C NMR (100 MHz, CDCl3): d 170.86, 169.89, 137.64, 132.06,
129.86, 129.38, 128.94, 127.17, 125.90, 109.54, 56.86, 38.09, 22.40.
IR (KBr) v (cm-1): 3292, 1600, 1587, 1572, 1501, 1480, 1449,
1440, 1410, 1282, 1237, 1078, 1062, 1020, 834, 779, 770, 702, 687.
C18H18Cl3NOSTi (450.63): calcd C 47.98, H 4.03, N 3.11. Found
C 47.82, H 4.04, N 3.03.
3.96. Found C 74.20, H 8.00, N 3.93. MS (EI) (m/z): 353 (M+).
(Z) - 1,3 - bis(4 - methoxyphenyl) - 3 - (2 - (propylthio)ethylamino)
prop-2-en-1-one (4i). The same procedur◦e as that for the prepara-
tion of 4a. Yield: 1.87 g (78%). M.p: 50–54 C. 1H NMR (300 MHz,
CDCl3): d 11.35 (s, 1 H), 7.90–7.87 (m, 2 H), 7.39–7.36 (m, 2 H),
6.98–6.88 (m, 4 H), 5.74 (s, 1 H), 3.86 (s, 3 H), 3.84 (s, 3 H), 3.41
(q, J = 6.6 Hz, 2 H), 2.63 (t, J = 6.3 Hz, 2 H), 2.38 (t, J =
7.2 Hz, 2 H), 1.55-1.48 (m, 2 H), 0.93 (t, J = 7.2 Hz, 3 H). 13C
NMR (75 MHz, CDCl3): d 187.56, 165.80, 161.71, 160.44, 132.88,
129.22, 128.88, 127.91, 113.86, 113.30, 93.44, 55.31, 55.26, 44.33,
34.05, 32.63, 22.86, 13.35. IR (KBr) v (cm-1): 2959, 2933, 2836,
1592, 1567, 1510, 1490, 1461, 1441, 1332, 1292, 1251, 1228, 1172,
1143, 1063, 1029, 841, 782. C22H27NO3S (385.52): calcd C 68.54,
H 7.06, N 3.63. Found C 68.30, H 7.36, N 3.63. MS (EI) (m/z):
385 (M+).
[(1Z,3Z)-1,3-diphenyl-3-(2-(isopropylthio)ethylimino) prop-1-
en-1-olate]Ti(IV)Cl3 (5b as an example for method B). To a
suspension of potassium hydride (KH) (0.21 g, 5.3 mmol) in
tetrahydrofuran (THF) (20 mL) was added a solution of 4b
(1.40 g, 4.4 mmol) in THF (10 mL) at -78 ◦C. The resulting
suspension was warmed to room temperature and stirred for 3 h.
After removal of the solvent under vacuum, CH2Cl2 (20 mL) was
added to the residue to give a yellow solution. It was then added
dropwise to a solution of TiCl4 (1.00 g, 5.3 mmol) in CH2Cl2
(30 mL) at room temperature, and the mixture was stirred for
16 h. The solid was filtered off and washed with CH2Cl2 (10 mL).
The combined organic solutions were concentrated under vacuum
to about 5 mL and then kept it at -30 ◦C for few a days. The solid
was collected to afford 5b as red-brown crystals. Yield: 0.90 g
(44%). 1H NMR (300 MHz, CDCl3): d 7.83 (d, J = 6.9 Hz,
2 H), 7.52–7.39 (m, 8 H), 6.40 (s, 1 H), 4.05 (d, J = 13.5 Hz,
2 H), 3.74–3.70 (m, 1 H), 3.16–2.85 (m, 2 H), 1.74–1.38 (m, 6 H).
13C NMR (100 MHz, CDCl3): d 170.72, 169.72, 137.65, 132.14,
131.99, 129.80, 129.34, 128.93, 127.19, 125.84, 109.53, 57.32,
42.16, 34.71, 23.35, 21.68. IR (KBr) v (cm-1): 2966, 1603, 1588,
1571, 1502, 1480, 1449, 1404, 1284, 1236, 1062, 1024, 1003, 833,
780, 769, 701, 639. C20H22Cl3NOSTi (478.69): calcd C 50.18, H
4.63, N 2.93. Found C 50.45, H 4.57, N 2.77.
(Z)-2-benzyl-1,3-diphenyl-3-(2-(propylthio)ethylamino) prop-2-
en-1-one (4j). The same procedure as◦that for the preparation
1
of 4a. Yield: 0.90 g (37%). M.p: 59–62 C. H NMR (300 MHz,
CDCl3): d 12.46 (s, 1 H), 7.33–7.21 (m, 8 H), 7.09–7.00 (m, 5 H),
6.71–6.68 (m, 2 H), 3.35 (s, 2 H), 3.16 (q, J = 6.6 Hz, 2 H), 2.58
(t, J = 6.9 Hz, 2 H), 2.31 (t, J = 7.2 Hz, 2 H), 1.52–1.45 (m,
2 H), 0.91 (t, J = 7.2 Hz, 3 H). 13C NMR (75 MHz, CDCl3):
d 196.15, 167.38, 143.20, 142.90, 133.82, 128.68, 128.40, 127.76,
127.75, 127.61, 127.51, 126.44, 125.00, 102.85, 44.55, 35.42, 34.02,
32.46, 22.90, 13.36. IR (KBr) v (cm-1): 3058, 3024, 2960, 2929,
2870, 1590, 1585, 1493, 1443, 1321, 1288, 1225, 1158, 1073, 1027,
781, 755, 699. MS (EI) (m/z): 415 (M+). HRMS: 415 (C27H29NOS).
(Z)-2-methyl-1,3-diphenyl-3-(2-(propylthio)ethylamino) prop-2-
en-1-one (4k). The same procedure as◦that for the preparation
1
of 4a. Yield: 0.92 g (41%). M.p: 48–57 C. H NMR (300 MHz,
CDCl3): d 12.19 (s, 1 H), 7.52–7.29 (m, 10 H), 3.17 (q, J = 7.2 Hz,
2 H), 2.57 (t, J = 6.9 Hz, 2 H), 2.31 (t, J = 6.9 Hz, 2 H), 1.52–1.45
(m, 5 H), 0.91 (t, J = 7.2 Hz, 3 H). 13C NMR (100 MHz, CDCl3):
d 195.21, 166.07, 142.97, 134.92, 128.89, 128.73, 128.71, 127.78,
127.50, 127.00, 98.33, 44.60, 34.02, 32.60, 22.90, 17.42, 13.33. IR
(KBr) v (cm-1): 3057, 2960, 2929, 2870, 1585, 1569, 1550, 1466,
1442, 1320, 1284, 1157, 1002, 987, 783, 703. C21H25NOS (339.49):
calcd C 74.29, H 7.42, N 4.13. Found C 74.01, H 7.52, N 4.05. MS
(EI) (m/z): 339 (M+).
[(1Z,3Z)-1,3-diphenyl-3-(2-(octylthio)ethylimino)prop-1-en-
1-olate]Ti(IV)Cl3 (5c). The same procedure as that for the prepa-
ration of 5a. Yield: 0.83 g (72%). 1H NMR (300 MHz, CDCl3): d
7.82 (d, J = 6.9 Hz, 2 H), 7.52–7.29 (m, 8 H), 6.39 (s, 1 H), 4.13–
4.04 (m, 2 H), 3.45–3.43 (m, 1 H), 3.24–3.17 (m, 1 H), 2.98–2.96
(m, 1 H), 2.73 (d, J = 6.0 Hz, 1 H), 1.95–1.85 (m, 2 H), 1.53–1.46
(m, 2 H), 1.31–1.28 (m, 8 H), 0.88 (t, J = 5.7 Hz, 3 H). 13C NMR
(75 MHz, CDCl3): d 170.72, 169.81, 137.64, 132.11, 132.00, 129.80,
129.34, 128.90, 127.15, 125.89, 109.47, 57.31, 39.71, 36.40, 31.73,
29.08, 29.06, 28.88, 28.18, 22.61, 14.08. IR (KBr) v (cm-1): 3220,
2954, 2925, 2853, 1686, 1602, 1591, 1573, 1506, 1487, 1450, 1442,
1285, 1238, 1077, 1062, 1591, 1573, 1506, 1487, 1450, 1285, 1238,
1077, 1062, 1025, 834, 778, 771, 693. C25H32Cl3NOSTi (547.07):
calcd C 54.71, H 5.88, N 2.55. Found C 54.21, H 5.49, N 2.44.
(R,Z) - 3 - (3 - methyl - 1 - (propylthio)butan - 2 - ylamino) -1,3 -
diphenylprop-2-en-1-one (4l). The same procedure as that for the
preparation of 4a. Yield: 1.50 g (32%). M.p: 58–67 ◦C. 1H NMR
(300 MHz, CDCl3): d 11.51 (d, J = 10.5 Hz, 1 H), 7.97–7.89 (m, 2
H), 7.48–7.37 (m, 8 H), 5.77 (s, 1 H), 3.45–3.36 (m, 1 H), 2.71–2.59
(m, 2 H), 2.30 (t, J = 6.9 Hz, 2 H), 2.02–1.92 (m, 2 H), 1.56–1.44
(m, 2 H), 1.00 (d, J = 6.6 Hz, 3 H), 0.90 (t, J = 6.6 Hz, 6 H). 13
C
NMR (75 MHz, CDCl3): d 188.26, 167.24, 140.14, 135.85, 130.68,
129.23, 128.33, 128.13, 127.04, 93.84, 59.32, 36.25, 34.85, 31.61,
31.54, 22.79, 19.77, 16.82, 13.41. IR (KBr) v (cm-1): 3060, 2960,
2930, 2872, 1584, 1569, 1478, 1443, 1333, 1303, 1224, 1143, 1055,
1025, 749, 702, 692. C23H29NOS (367.55): calcd C 75.16, H 7.95,
N 3.81. Found C 74.62, H 8.13, N 3.88. MS (EI) (m/z): 367 (M+).
[(1Z,3Z)-1,3-diphenyl-3-(2-(octadecylthio)ethylimino) prop-1-
en-1-olate]Ti(IV)Cl3 (5d). The same procedure as that for the
preparation of 5a. Yield: 0.51 g (92%). 1H NMR (300 MHz,
CDCl3): d 7.82 (d, J = 6.3 Hz, 2 H), 7.52–7.29 (m, 8 H), 6.39
(s, 1 H), 4.17–4.04 (m, 2 H), 3.45 (t, J = 14.4 Hz, 1 H), 3.20
[(1Z,3Z)-1,3-diphenyl-3-(2-(methylthio)ethylimino)prop-1-en-
1-olate]Ti(IV)Cl3 (5a as an example for method A). To a solution
of TiCl4 (0.51 g, 2.7 mmol) in toluene (7 mL) at -78 ◦C was
This journal is
The Royal Society of Chemistry 2009
Dalton Trans., 2009, 8945–8954 | 8951
©

(t, J = 9.9 Hz, 1 H), 3.00–2.96 (m, 1 H), 2.73 (d, J = 6.3 Hz, 1 H),
1.94–1.82 (m, 2 H), 1.52–1.26 (m, 32 H), 0.88 (t, J = 6.9 Hz,
3 H). 13C NMR (75 MHz, CDCl3): d 170.71, 169.81, 137.64,
132.12, 131.99, 129.79, 129.33, 128.90, 127.14, 125.82, 109.46,
57.29, 39.72, 36.40, 31.91, 29.69, 29.64, 29.63, 29.54, 29.43, 29.35,
29.12, 28.88, 28.19, 22.68, 14.11. IR (KBr) v (cm-1): 3200, 2920,
2850, 1603, 1591, 1573, 1507, 1488, 1450, 1285, 1238, 1077, 1062,
1025, 833, 779, 771, 702. C35H52Cl3NOSTi (689.08): calcd C 61.00,
H 7.61, N 2.03. Found C 60.59, H 7.46, N 1.83.
1452, 1408, 1337, 1284, 1236, 1186, 1120, 1060, 1018, 843, 810.
C22H26Cl3NOSTi (506.74): calcd C 52.14, H 5.17, N 2.76. Found
C 51.50, H 5.22, N 3.23.
[(1Z,3Z) - 1,3 - bis(4 - methoxyphenyl) - 3 - (2 - (propylthio)ethyl
imino)prop-1-en-1-olate]Ti(IV)Cl3 (5i). The same procedure as
1
that for the preparation of 5a was used. Yield: 1.31 g (94%). H
NMR (300 MHz, CDCl3): d 7.78 (d, J = 8.4 Hz, 2 H), 7.23 (d, J
= 8.4 Hz, 2 H), 7.00 (d, J = 8.4 Hz, 2 H), 6.90 (d, J = 8.4 Hz, 2
H), 6.30 (s, 1 H), 4.09 (brs, 2 H), 3.87 (s, 3 H), 3.85 (s, 3 H), 3.41
(brs, 1 H), 3.19 (brs, 1 H), 2.96 (s, 1 H), 2.75 (d, 1 H), 1.96–1.91
(m, 2 H), 1.12 (t, J = 7.5 Hz, 3 H). 13C NMR (75 MHz, CDCl3):
d 163.77, 162.61, 155.81, 153.58, 122.71, 122.19, 121.19, 120.74,
117.50, 107.56, 107.32, 101.59, 50.29, 48.51, 48.47, 34.49, 29.53,
14.78, 6.54. IR (KBr) v (cm-1): 3202, 2839, 1669, 1603, 1589, 1566,
1508, 1478, 1438, 1420, 1336, 1302, 1258, 1240, 1175, 1124, 1060,
1026, 917, 846, 811, 784. C22H26Cl3NO3STi (538.74): calcd C 49.05,
H 4.86, N 2.60. Found C 48.32, H 5.03, N 3.26.
[(1Z,3Z)-1,3-diphenyl-3-(2-(phenylthio)ethylimino)prop-1-en-
1-olate]Ti(IV)Cl3 (5e). The same procedure as that for the prepa-
1
ration of 5b. Yield: (0.31 g, 50%). H NMR (400 MHz, CDCl3,
toluene): d 7.81–7.16 (m, 18 H), 6.40 (s, 1 H), 4.25 (s, 2 H), 3.49
(t, J = 4.8 Hz, 2 H), 2.35 (s, 1.7 H). 13C NMR (100 MHz, CDCl3,
toluene): d 171.01, 170.11, 137.49, 132.81, 132.06, 131.95, 129.92,
129.40, 129.31, 129.02, 128.93, 128.49, 128.20, 127.45, 127.16,
125.86, 125.28, 109.61, 57.50, 35.04, 21.45. IR (KBr) v (cm-1):
3212, 1686, 1588, 1572, 1501, 1483, 1450, 1440, 1282, 1236, 1062,
1026, 766, 742, 698, 687. C23H20Cl3NOSTi(510.98): calcd C 53.88,
H 3.93, N 2.73. Found C 53.68, H 4.19, N 2.20.
[(1Z,3E)-2-benzyl-1,3-diphenyl-3-(2-(propylthio)ethylimino)
prop-1-en-1-olate]Ti(IV)Cl3 (5j). The same procedure as that for
[(1Z,3E) - 1 - phenyl - 3 - (2 - (propylthio)ethylimino)but - 1- en - 1-
olate]Ti(IV)Cl3 (5f). The same procedure as that for the prepara-
tion of 5a. Yield: 1.32 g (79%). 1H NMR (400 MHz, CDCl3): d 7.83
(d, J = 7.6 Hz, 2 H), 7.49–7.41 (m, 3 H), 6.34 (m, 1 H), 4.20 (d, J
= 4.2 Hz, 2 H), 3.42–3.33 (d, 2 H), 2.97–2.91 (d, 2 H), 2.31 (s, 3 H),
1.97–1.93 (m, 2 H), 1.15 (t, J = 7.6 Hz, 3 H). 13C NMR (100 MHz,
CDCl3): d 169.07, 169.02, 132.06, 131.81, 128.96, 128.92, 126.98,
110.10, 55.07, 41.44, 35.93, 23.79, 21.74, 13.53. IR (KBr) v (cm-1):
2964, 1598, 1575, 1504, 1487, 1447, 1408, 1336, 1274, 1243, 1183,
1101, 1075, 1028, 924, 769, 688. C15H20Cl3NOSTi (416.62): calcd
C 43.24, H 4.84, N 3.36. Found C 42.79, H 5.08, N 3.44.
1
the preparation of 5b. Yield: 0.73 g (59%). H NMR (400 MHz,
CDCl3): d 7.58–6.59 (m, 15 H), 3.98 (brs, 1 H), 3.83–3.71 (m, 2 H),
3.50–3.40 (m, 2 H), 3.06 (brs, 1 H), 2.92 (brs, 1 H), 2.62 (brs, 1 H),
1.94–1.87 (m, 2 H), 1.11 (t, J = 7.6 Hz, 3 H). 13C NMR (100 MHz,
CDCl3): d 174.35, 171.90, 139.57, 135.89, 134.16, 130.37, 129.01,
128.64, 128.46, 128.30, 128.28, 128.05, 126.19, 125.70, 119.88,
57.93, 41.58, 37.03, 35.59, 21.75, 13.53. IR (KBr) v (cm-1): 2961,
2928, 1599, 1566, 1495, 1468, 1442, 1328, 1262, 1157, 1141, 1072,
811, 699. C27H28Cl3NOSTi (568.81): calcd C 57.01, H 4.96, N 2.46.
Found C 56.70, H 5.02, N 2.23.
[(1Z,3Z) - 1 - phenyl - 3 - (2 - (propylthio)ethylimino) - 3- (4 -
[(1Z,3E)-2-methyl-1,3-diphenyl-3-(2-(propylthio)ethylimino)
prop-1-en-1-olate]Ti(IV)Cl3 (5k). The same procedure as that for
the preparation of 5b. Yield: 0.75 g (66%).1H NMR (400 MHz,
CDCl3): d 7.57–7.42 (m, 8 H), 7.19 (d, J = 6.4 Hz, 2 H), 4.05–3.90
(m, 2 H), 3.40 (brs, 1 H), 3.12 (brs, 1 H), 2.90 (brs, 1 H), 2.66
(brs, 1 H), 1.96–1.87 (m, 2 H), 1.80 (s, 3 H), 1.11 (t, J = 7.2 Hz,
3 H). 13C NMR (100 MHz, CDCl3): d 174.42, 170.12, 137.20,
134.24, 130.35, 129.63, 129.36, 128.97, 128.29, 125.31, 117.55,
58.18, 41.47, 35.84, 21.74, 19.58, 13.52. IR (KBr) v (cm-1): 3220,
2963, 1583, 1570, 1502, 1474, 1440, 1330, 1158, 1073, 1018, 799,
783, 700. C21H24Cl3NOSTi (492.71): calcd C 51.19, H 4.91, N 2.84.
Found C 51.71, H 5.01, 2.56.
(trifluoromethyl)phenyl)prop-1-en-1-olate]Ti(IV)Cl3
(5g). The
same procedure as that for 5a but using the crude product
of diketone 2c and amine 3f. The pure 5g was isolated by
recrystallization from toluene. Yield: 0.20 g (42%). 1H NMR
(300 MHz, CDCl3): d 7.84–7.79 (m, 4 H), 7.52–7.40 (m, 5 H),
6.32 (s, 1 H), 4.15–3.96 (m, 2 H), 3.44–3.42 (m, 1 H), 3.22 (t,
J = 10.2 Hz, 2 H), 2.98–2.96 (m, 1 H), 2.75 (d, J = 13.2 Hz,
1 H), 2.00–1.90 (m, 2 H), 1.14 (t, J = 8.7 Hz, 2 H). 13C NMR
(100 MHz, CDCl3): d 170.54, 169.19, 141.15, 132.33, 132.17,
131.89, 131.84, 129.00, 127.24, 126.49, 126.18 (q, J = 271 Hz),
108.50, 57.30, 41.62, 36.34, 21.75, 13.54. 19F NMR (282 MHz,
CDCl3): d -63.34. IR (KBr) v (cm-1): 3309, 2967, 2937, 1599,
1577, 1515, 1502, 1488, 1455, 1406, 1322, 1159, 1125, 1106, 1072,
1016, 847, 773. C21H21Cl3F3NOSTi (546.68): calcd C 46.14, H
3.87, N 2.56. Found C 46.56, H 4.28, N 2.59.
[(1Z,3Z)-3-((R)-3-methyl-1-(propylthio)butan-2-ylimino)-1,3-
diphenylprop-1-en-1-olate]Ti(IV)Cl3 (5l). The same procedure as
that for the preparation of 5b. Yield: 0.2 g (19%).1H NMR
(300 MHz, CDCl3): d 7.82 (d, J = 7.2 Hz, 2 H), 7.54–7.21 (m,
8 H), 6.36 (s, 1 H), 4.04 (d, J = 9.3 Hz, 2 H), 3.48 (m, 2 H), 3.25
(brs, 1 H), 2.93 (brs, 1 H), 2.54 (brs, 1 H), 1.90–1.86 (m, 2 H), 1.12
(t, J = 7.2 Hz, 3 H), 0.76 (d, J = 5.7 Hz, 6 H). 13C NMR (75 MHz,
CDCl3): d 172.63, 170.00, 139.58, 132.06, 129.56, 129.38, 129.02,
128.86, 127.21, 126.79, 124.51, 109.79, 73.68, 44.07, 40.28, 33.25,
22.21, 20.10, 19.61, 13.51. IR (KBr) v (cm-1): 3309, 2963, 1587,
1569, 1467, 1332, 1282, 1231, 1125, 1063, 1024, 1000, 762, 703,
683. C23H28Cl3NOSTi (520.77): calcd C 53.05, H 5.42, N 2.69.
Found C 53.19, H 5.33, N 2.65.
[(1Z,3Z)-3-(2-(propylthio)ethylimino)-1,3-di-p-tolylprop-1-en-
1-olate]Ti(IV)Cl3 (5h). The same procedure as that for the prepa-
1
ration of 5a was used. Yield: 1.0 g (88%). H NMR (300 MHz,
CDCl3): d 7.70 (d, J = 7.2 Hz, 2 H), 7.32–7.15 (m, 6 H), 6.35 (s,
1 H), 4.13–4.03 (m, 2 H), 3.42 (brs, 1 H), 3.19–3.15 (m, 1 H), 2.94
(brs, 1 H), 2.73 (brs, 1 H), 2.42 (s, 3 H), 2.38 (s, 3 H), 1.96–1.91
(m, 2 H), 1.13 (t, J = 7.5 Hz, 3 H). 13C NMR (75 MHz, CDCl3):
d 171.02, 169.89, 142.79, 140.03, 134.69, 129.86, 129.61, 129.30,
127.14, 125.87, 109.19, 57.31, 41.46, 36.42, 21.75, 21.62, 21.36,
13.52. IR (KBr) v (cm-1): 3212, 2923, 1607, 1588, 1567, 1482,
8952 | Dalton Trans., 2009, 8945–8954
This journal is
The Royal Society of Chemistry 2009
©

Typical procedure for ethylene polymerization. (Using complex 5b
as a representative example.)
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Under 1 atm ethylene atmosphere, to a solution of MMAO
(1.6 mL, 1.9 M in toluene) in toluene (50 mL, saturated with
ethylene) was added a solution of complex 5b (3 mmol, 3 mmol
mL-1 in toluene) at 30 ◦C. The polymerization was carried out
for 10 min and then quenched with concentrated HCl in ethanol
(400 mL, HCl/EtOH, 1 : 20, v/v). The precipitated polymer was
collected, washed with ethanol, and then dried overnight in a
vacuum oven at 50 ◦C to constant weight.
Typical procedure for ethylene copolymerization
Under 1 atm ethylene atmosphere, to a solution of MMAO
(1.6 mL, 1.9 M in toluene) and the desired amount of comonomer
in toluene (50 mL, saturated with ethylene) was added a solution
of complex 1 (3 mmol, 3 mmol mL-1 in toluene) at 30 ◦C. The
polymerization was carried out for 10 min and then quenched with
concentrated HCl in ethanol (400 mL, HCl/EtOH, 1 : 20, v/v).
The precipitated polymer was collected, washed with ethanol, and
then dried overnight in a vacuum oven at 50 ◦C to constant weight.
Acknowledgements
We are grateful for the financial support from the National Natural
Science Foundation of China (no. 20821002 and 20772139), the
Major State Basic Research Development Program (grant no.
2006CB806105), and NSFC and the RGC of Hong Kong Joint Re-
search Scheme (grant no. 20710011 to YT and N_CUHK446/06
to ZX).
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9 CCDC 734045 (4m) and CCDC 734047 (5b) contain the supplementary
crystallographic data.
10 The structure of enamine 4g, isolated by hydrolysis of 5g, was
determined by X-ray analysis. 5g was recrystallized in toluene from
two titanium complex isomers, readily prepared from TiCl4 and
mixed enamines obtained by condensation of diarylketone 2c with
amine 3f.
11 Comonomer incorporation ratio of 1-octene and 1-hexene was were
13
determined by C NMR and calculated according to the literature
method, see: (a) J. C. Randall, JMS-Rev. Macromol. Chem. Phys., 1989,
29, 201; (b) E. T. Hsieh and J. C. Randall, Macromolecules, 1982, 15,
1402.
12 Comonomer incorporation ratio of cyclopentene was determined by 13
C NMR and calculated according to the method as described in ref. 5c.
13
13 Comonomer incorporation ratio of norbornene was determined by
C NMR and calculated according to the literature method: I. Tritto,
C. Marestin, L. Boggioni, L. Zetta, A. Provasoli and D. R. Ferro,
Macromolecules, 2000, 33, 8931.
8954 | Dalton Trans., 2009, 8945–8954
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